Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/40—Dyes ; Pigments
  • C11D3/42—Brightening agents ; Blueing agents

Definitions

• the present invention relates to liquid detergent compositions which contain a fluorescer or ultraviolet (UV)-absorbent material.
• the invention also extends to a process for preparation of these materials.
• the colour of fabrics can be altered during the laundering process or during wear or use by photo fading.
• US-A-4 788 054 teaches the use of N-phenylphthalisomides as ultraviolet radiation absorbers for cotton, wool, polyester and rayon.
• Fabric care compositions comprising a water dispersible / water soluble copolymers which prevent photofading are disclosed in EP-A-0 523 956.
• WO-A-96/03369 discloses the use of butylated hydroxy toluene for the protection of surfaces from physical and chemical degradation.
• the present invention provides the solution of formulating liquid detergent compositions in substantially transparent form by incorporating less than 5% by weight of builder salts, based on the weight of the total composition.
• the present invention provides the solution of formulating the liquid detergent compositions in substantially clear form by incorporating a water-miscible polar organic solvent.
• European patent application WO 92/06172 discloses formulation of a highly built aqueous liquid detergent containing an optical brightener and a polyhydroxy fatty acid amide, wherein the brightener is added to the detergent composition in admixture with the polyhydroxy fatty acid amide.
• the compositions disclosed contain mixtures of builders selected from a very wide range, present in at least 10% by weight, usually much more.
• liquid detergent composition comprising:
• the present invention provides an aqueous liquid detergent composition
• aqueous liquid detergent composition comprising surfactant material, sunscreen and a water-miscible polar organic solvent, the composition being substantially transparent in the absence of opacifier.
• a third aspect of the present invention provides a process of preparing a composition according to the first or second aspect of the present invention, the process comprising forming a premix containing water, at least some of the sunscreen and at least some of the organic solvent to form a premix and effecting admixture of the premix with the other components of the composition.
• the premix will contain substantially all of sunscreen and substantially all of the organic solvent which will be present in the final composition, preferably with at least some of the water.
• the invention further relates to the use of any detergent composition according to the first aspect of the present invention to reduce the photofading of coloured fabrics and to enhance the UV barrier provided by fabric.
• the term "sunscreen” means, in the widest sense, a material which when deposited on the fabric at the use concentration absorbs ultraviolet radiation to at least a measurable extent, whether or not it is also a fluorescer/optical brightener. Preferably it has a molar extinction coefficient of greater than 2000 mol "1 cm " ⁇
• the sunscreen agent used in the composition according to the second aspect of the invention is preferably one of those materials described in EP-A-728 749 or in the aforementioned article of D. Reiner et al.
• the materials described in EP-A-728 749 include those having the general formula (I) as hereinafter defined.
• the weight ratio of water-miscible polar organic solvent to water in the premix is preferably from 1 :9 to 9: 1, more preferably from 1 :5 to 5: 1 and most preferably from 1 :2 to 2: 1.
• opacifier is a material which is added to a composition in order to reduce the transparency of the composition.
• compositions of the invention preferably contain detergent-active compounds
• surfactants may optionally contain hydrotropes, bleaching components, enzymes and other active ingredients to enhance performance and properties. They may also contain a water soluble sunscreen.
• liquid detergent compositions of the present invention are substantially transparent in the absence of opacifier.
• the transparency of the compositions was determined at ambient temperature by the following method.
• the transparency of the liquid detergent compositions was determined at ambient temperature by monitoring the transmission of light through the liquid in 1cm path length quartz cells on a Perkin Elmer Lambda 16 UV/visible spectrometer.
• the instrument was calibrated using double distilled water.
• Double distilled water was carefully transferred into both reference and sample quartz cells via a Pasteur pipette to avoid the formation of micro bubbles which could interfere with the measurements.
• the cells were placed in the spectrometer, and the instrument calibrated over the wavelength range 800-850 nm using an automatic programme.
• the slit width was fixed at 0.25 nm. This set the value for double distilled water to 100% at all wavelengths from 800-850nm.
• the cell was flushed three times with the experimental sample and refilled therewith using a Pasteur pipette.
• the transmission of the sample at 820nm was recorded. This method was adapted for all transparency measurements, the compositions of the present invention typically exhibited a transmission of at least 80%.
• Typical transmission values in the range 80 to 99.55 were obtained with examples of the invention. Samples with transmissions of greater than or equal to 80% transmission are considered to be transparent.
• compositions of the present invention exhibit a transparency of 85% transmission, most preferably 85% transmission.
• the liquid detergent compositions may be isotropic, or less frequently, anisotropic.
• the latter is formed in the present of a micro-structure of surfactant molecules within the detergent composition.
• the viscosity of the liquid detergent composition 1-10,000 cps, preferably 100-1000 cps.
• a sunscreen must absorb UV radiation to at least a measurable degree when deposited on a fabric at the use concentration. However, it is preferably a UV absorber with a molar extinction coefficient of greater than 2000 modern "1 . Most preferably a sunscreen is a material which absorbs UV in the UVA and UVB region of the spectrum. It is especially preferred if the sunscreen is capable of reducing the transmission of harmful UV rays through fabrics and thus increasing the ultraviolet protection factor of the fabric. In the context of the first aspect of the present invention, the level of sunscreen is preferably from 0.01 wt% to 5 wt% of the total composition, more preferably from 0.05 wt% to
• the sunscreen is preferably incorporated in an amount of from 0.005% to 0.5% by weight of the total composition, more preferably from 0.05% to 0.2%.
• the sunscreens used in the compositions of the first aspect of the present invention and preferably also in those of the second aspect of the invention, have a structure of the general formula (I):-
• R 3 is optionally substituted alkyl or optionally substituted aryl
• R is M, optionally substituted alkyl or optionally substituted aryl
• R 5 is hydrogen, optionally substituted alkyl, optionally substituted aryl or - NR 7 R g in which R 7 and R 8 , independently, are hydrogen, CH 3 , optionally substituted alkyl or optionally substituted aryl, or R 7 and R 8 together with the nitrogen atom to which they are attached, form a heterocyclic residue;
• R 8 is hydrogen, optionally substituted alkyl or optionally substituted aryl, provided that R 8 is not carboxymethyl or hydroxymethyl;
• R 2 is independently hydrogen, optionally substituted alkyl, optionally substituted aryl,
• nj and n 2 are O or 1.
• the sunscreen is of formula II, formula III or formula IV:-
• compositions according to the second (and preferably also the first) aspect of the present invention must comprise water-miscible polar organic solvent which is preferably an alcohol such as methanol, ethanol or propanol, or a polyol such as propylene glycol, glycerol, sorbitol or else acetone or mixtures of any of these solvents. It is preferably present from 0.01% to 40% by weight of the total composition, more preferably from
• the weight ratio of water-miscible polar organic solvent to water in the premix is preferably from 1:9 to 9:1, more preferably from 1:5 to 5:1 and most preferably from 1:2 to 2: 1.
• the liquid detergent compositions according to the first (and preferably also the second aspect) of the invention contain less than 5% by weight total of builder salts.
• the total amount of detergency builder in the compositions is preferably less than 4.5 wt%, preferably less than 2.5 wt%. It is especially preferred that the compositions are substantially free from builder salts.
• Inorganic builders that may be present within the above total amount include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), or in EPO 384 070 A (Unilever), and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 514B (Hoechst).
• Inorganic phosphate builders for example, sodium orthophosphate, pyrophosphate and tripolyphosphate may also be present within the above total amount of builder salts.
• Organic builders that may be present within the above stated amount of builder include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
• polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
• monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates
• an organic builder in the above mentioned amount, is present it is especially preferred if it is a citrate and/ or an acrylic polymer, more especially an acrylic/maleic copolymer.
• Builders both inorganic and organic, present in amounts within the above stated total, are preferably present in alkali metal salt, especially sodium salt, form.
• liquid detergent compositions of the invention may contain detergent-active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
• surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
• detergent-active compounds are available and are fully described in the literature, for example, in "Surface- Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
• the preferred detergent-active compounds that can be used are soaps and synthetic non- soap anionic and nonionic compounds.
• the detergent compositions of the invention preferably contain an anionic surfactant.
• a preferred anionic surfactant is alkylbenzene sulphonate, particularly linear alkylbenzene sulphonate. Alkylbenzene sulphonates having an alkyl chain length of C 8 -C ]5 are especially preferred. However, any conventional anionic surfactant may be used.
• the level of anionic surfactant is from 5 wt% to 50 wt%, more preferably 10 wt% to 40 wt%, most preferably from 15 wt% to 35 wt% .
• anionic surfactants suitable for use with the invention are well-known to those skilled in the art.
• Examples include primary and secondary alkyl sulphates, particularly C 8 -C 15 primary alkyl sulphates; alkyl ether sulphates and sulphonates, especially with a C 8 -C 15 alkyl chain and four or less ethylene oxide ether groups; paraffin sulphonates, olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; alkyl acyl-N- (hydroxy) alkyl glucamine sulphates, alkyl ester sulphonates and fatty acid ester sulphonates.
• Sodium salts are generally preferred.
• compositions of the invention may also contain nonionic surfactant.
• Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
• Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
• the level of nonionic surfactant is from 1 wt% to 35 wt%. It is preferable if the ratio of anionic surfactant to nonionic surfactant is equal to or greater than 2:3, more preferably greater than or equal to 3:2, most preferably equal to or greater than 4:1.
• alkylether sulphate anionic surfactant when the total amount of alkylether sulphate anionic surfactant is from 1% to 60%), more especially from 10% to 20% by weight of the total composition;
• polyalkoxylated nonionic surfactant when the total amount of polyalkoxylated nonionic surfactant is from 2% to 40%, more especially from 5% to 15% by weight of the total composition.
• detergent-active compound surfactant
• amount present will depend on the intended use of the detergent composition.
• surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
• nonionic surfactants that are not ethoxylated such as cocomonoethanolamide, or which are not highly ethoxylated.
• the total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate.
• Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with small amounts (e.g. from 1% to 2% by weight) of soap.
• any component has a counter anion which is not an alkali metal but is a nitrogen containing counter-ion such as monoethanolamine or triethanolamine, then usually it is incorporated at a lower level (e.g. ⁇ 1% by weight of the composition) as compared to an alkali metal ion.
• compositions of the present invention may suitably comprise one or more enzymes.
• Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in liquid detergent compositions.
• Preferred proteolytic enzymes are catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin. Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention. Examples of suitable proteolytic enzymes are the subtilisins, which are obtained from particular strains of B. subtilis and B. licheniformis. such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Gist-Brocades N. V., Delft, Holland, and Alcalase (Trade Mark), as supplied by Novo Industri A/S, Copenhagen, Denmark.
• protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase
• Detergency enzymes are preferably employed in liquid form in amounts of from about 0.1 to about 3.0 wt%. Granular forms of detergency enzymes may be used if they are compatible with the transparent appearance of the liquid detergent composition.
• liquid detergent compositions of the present invention may optionally comprise a hydrotrope in a suitable amount.
• Suitable hydrotropes include urea and short alkyl chain benzene or xylene sulphonic acids amongst others. Typically the hydrotrope may be present in an amount of 0.1% to 15% by weight.
• Other materials that may be present in detergent compositions of the invention include sodium silicate; lather control agents or lather boosters as appropriate; soil release promoters; anti-dye transfer agents; soil anti-redeposition agents; proteolytic, cellulases lipolytic enzymes; enzyme stabilisers such as borax or alkali metal borates, especially in combination with a polyol such as glycerol or sorbitol; solvents; dyes; perfumes; foam controllers; fabric softening compounds, fluorescers, bleaches and deflocculating polymers.
• compositions may also contain a bleach or combinations of a bleach and/or fluorescent whitening agent such as those of the Ciba Tinopal family, for example Tinopal CBS-X, Tinopal PLC (DBFBP), Tinopal DCS
• a bleach and/or fluorescent whitening agent such as those of the Ciba Tinopal family, for example Tinopal CBS-X, Tinopal PLC (DBFBP), Tinopal DCS
• the composition may contain both at least one ultraviolet absorbing material as claimed in EP-A-0 728 749 (e.g. Tinosorb FD) and one or more conventional optical brighteners, such as those of the DSBP family, i.e. Tinopal CBS-X, or those of the stilbene family, i.e. e.g. Tinopal DMS-X, Tinopal AMS-GX, Tinopal TBM-GX and Tinopal UNPA or brighteners of other suppliers with identical structures, and/or cominbations with hydrophobic brighteners such as Tinopal SWN or Tinopal SOP.
• the weight ratio of total ultraviolet absorbing material to total optical brighteners/fluorescers is preferably from
• polymers for promoting soil release and/or dye transfer inhibition are especially preferred, e.g. PVP or PVP/VI, Sokolan HP22 (ex BASF), TEPA 105 (ex Texaco), modified (e.g. amino-modified) polymethylsiloxanes such as APDMS (ex Rhone Poulenc) or ethoxylated polysiloxanes such as Dimethicone Copolyol 190 (ex Dow Corning), as well as anionic polymers based on sodium carboxymethylcelluloseose, e.g the Tylose range (ex Hoechst), Narlex H100, Narlex H1200, (ex National Starch) and Alcosperse 725 (ex Alco).
• liquid detergent compositions of the present invention may optionally comprise an opacifier.
• an opacifier it is an essential feature of the present invention that the compositions are substantially transparent it the absence of an opacifier.
• an opacifier it is present in an amount of from 0.1 to 5% by weight.
• Suitable opacifiers are well-known in the art and include, for example, polymer latices.
• the liquid detergent composition when diluted in the wash liquor (during a typical wash cycle) will give a pH of the wash liquor from 7 to 10.5.
• liquid detergent compositions according to the first (and preferably second) aspects of the present invention are preferably prepared by the method according to the third aspect of the invention.
• they may be prepared by any suitable method, for example, by admixing the essential and optional ingredients thereof in any order to provide transparent liquid compositions (in the absence of opacifier) containing components in the requisite concentrations.
• Liquid compositions according to the present invention can also be in compact form which means it will contain a lower level of water compared to a conventional liquid detergent. Even if the method according to the third aspect of the invention is not employed, the sunscreen is preferably added at the beginning of the preparation.
• compositions of the present invention are suitable for use as handwashing compositions, machine washing comparisons and compositions intended to be applied directly to the substrate to be treated (e.g. in the treatment of curtains, sun hats, window blinds, umberallas, parasols and tents etc.). Also fabric conditioning compositions, in a clear form, may be provided.
• the compositions of the present invention are suitable for treating any material or object for which the level of sun protection afforded is required to be improved, but especially for laundry washing.
• Example 1 Transparent liquid detergent composition.
• the components were mixed in the order given above by mechanical stirring using an overhead stirrer.
• the sunscreen was dissolved in water prior to addition to the composition.
• Prior to the addition of the preservative and the perfume the pH of the composition was adjusted from approximately pH 2.20 to approximately pH 7.0 by the addition of a small amount of 47% NaOH solution (42°C). After the addition of all components and mixing was complete the composition was cooled to ambient and the weight of the composition returned to 100% by replacing water lost during preparation with demineralised water.
• compositions were transparent liquid detergent compositions having a pH of approximately 7.4 at ambient temperature. * l Sodium alkyl benzene sulphonate is produced by in-situ neutralisation of the corresponding acid. (Isorchem 113 93% active) C 10 -C 13 linear alkyl benzene sulphonic acid availble from Enichem.
• Example 2 Addition of builder salts to Example 1
• De-mineralised water was added to the beaker and stirred.
• Fluorescer was added and then stirred until partly dissolved. However, the remaining solids dissolved after a few minutes (water at about 20°C) giving a clear yellow solution.
• LES (27%) was added and the solution became cloudy. NaOH was next added and the solution became slightly less cloudy and less yellow. Next, the nonionic surfactant was added the solution was warmed to facilitate dissolution. After about 10 minutes with temperature up to about 40°C, the solution became clear and very pale yellow.
• the LAS was added in acid form slowly and the solution became cloudy again after adding about half the LAS acid. More NaOH was added until the solution became clear. The rest of LAS acid was added and the pH was adjusted to 7, giving a cloudy product. When the pH was increased to 8, the product became totally clear. However, on cooling towards ambient, the product became slightly cloudy again. Perfume was added and the product was allowed to cool to ambient. Heating the product again to about 45°C gave a clear product which became slightly cloudy again on cooling at about 30°C. The formula can be manipulated to give a totally clear product if required.
• Nonionic surfactant 9EO) 4.1%
• Tinopal 5BM-GX (optical brightener) 0.15%
• Sorbitol/Borax were dissolved in demineralised water. After becoming clear the sodium citrate, propylene glycol and sodium hydroxide were added. Before the Tinopal 5BM- GX, the surfactants were dosed to the alkaline solution, followed by the dosage of the enzymes and the PVP (K15). Tinosorb was dissolved by slow addition under stirring to a mixture of propylene glycol and demineralised water (1:1) to a final concentration of 1%. A volume required to get 0.05% by weight level in the final liquid product was added to the liquid under stirring. Using this method no additional heating was required.

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• 1998
  • 1998-07-01 US US09/108,665 patent/US6090372A/en not_active Expired - Fee Related
  • 1998-07-02 WO PCT/EP1998/004221 patent/WO1999003963A1/en active IP Right Grant
  • 1998-07-02 EP EP98942523A patent/EP0994937B1/de not_active Expired - Lifetime
  • 1998-07-02 TR TR2000/00442T patent/TR200000442T2/xx unknown
  • 1998-07-02 DE DE69804618T patent/DE69804618T2/de not_active Expired - Lifetime
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  • 1998-07-02 CA CA002295482A patent/CA2295482C/en not_active Expired - Fee Related
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  • 1998-07-02 BR BRPI9810888-3A patent/BR9810888B1/pt not_active IP Right Cessation
  • 1998-07-14 AR ARP980103409A patent/AR013208A1/es active IP Right Grant
• 2000
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